Treatment of cellulosic materials



Patented July 1938 TREATMENT OF CELLULOSIC MATERIALS Georges Rlvat,Lyons, France, asslgnor to Henry Dreyfus, London, England No Drawing,Application November 5, 1935, Serial No. 48,283. In France November 13,1934 11 Claims.

The present invention relates to improvements in the coloration oftextile materials, especially cellulosic materials.

As is well known, materials consisting of natural or regeneratedcellulose have an afiinity for the cotton colors and little or noaflinity for the acid colors. Basic colors are usually dyed or printedon such materials with the aid of a tannin mordant. In a similar way,cellulose acetate artificial silk has an affinity for the basic colorsand little or no afiinity for the acid and direct cotton colors. Thepresent invention is concerned with treating materials made of orcontaining natural or regenerated cellulose or cellulose derivatives forthe purpose of modifying the existing dyeing affinities of thesematerials and with fixing dyestuffs on the materials. Cellulosicmaterials may be, for example, natural cellulose fibers such as cotton,linen, jute or ramie, or regenerated cellulose as, for example, viscose,cu-= prammonium and nitrocellulose artificial silks, or cellulosederivatives, for example cellulose acetate, cellulose formate, cellulosepropionate or other esters of cellulose, or cellulose eth-ers, forexample methyl, ethyl or benzyl cellulose, or mixed cellulosederivatives, for example mixed ethers. mixed esters or mixedether-esters. Again animal fibers, e. g. natural silk, may be colored bythe new process.

Broadly the invention comprises incorporating in the materials a complexnitrogen-containing organic compound, preferably of resin character, byinteraction, on the materials, of two or more appropriate reagents, oneor more of which contain the requisite nitrogen. A dyestufi is appliedto the materials either in admixture with one or more of the reagents orseparately at a later stage, e. g. after the formation of the complexnitrogenous organic compound on the material.

Incorporation of the complex nitrogen-containing organic compounds innatural or regenerated cellulose by the above method generally confersupon the latter an affinity, or increases any existing affinity, for thebasic and acid colors, and decreases or suppresses entirely theiraffinity for the direct cotton colors, Viewed from the point of view ofthe basic and acid colors, the invention may therefore be considered asa mordanting of the materials, while from the point of view of thedirect cotton colors, it may be considered as a reserving process.Similar observations apply, mutatis mutandis, to the cellulosederivative materials.

The reagents capable of yielding the complex nitrogenous compound may beapplied uniformly over the entire material as, for example, by applyingthem by a bath treatment or by mechanicalimpregnation methods, forexample by means of a padding mangle, but the most important applicationof the new process consists in modifying the dyeing affinities of thematerials under treatment locally so as to produce pattern effects. Bysuchlocal application, fabrics or other materials may be produced havingthe property of producing cross-dyed effects directly. For exampleimmersion of such materials in a single bath containing, for example,either an acid or a direct cotton dye produces a fabric having acoloration only locally on the material, either the treated portion orthe untreated portion of the material remaining uncolored according tothe character of the dyestuff applied.

Again by applying a dyestuff in admixture with the resin-formingreagents valuable fast colorations, uniform or local, may be produced,for example with dyestuffs having normally no afiinity for the material.

If desired the coloring matter may also be applied locally, so as tofall at least in part on parts of the material to which the reagentshave been applied. A wide range of pattern effects may thus be produced.For example a fabric printed with the reagents in an fall-over pattern,e. g. of small spots or the like, may be over-printed in a large floralor geometric pattern with a dyestuff having affinity for either theunprinted material or for the complex nitrogenous compound.

As previously indicated, the invention particularly contemplates theincorporation in the materials of synthetic resins containing nitrogen.The

synthetic resins may, for example, be produced by the condensation ofaldehydic, or ketonic bodies, for example formaldehyde, acetaldehyde,benzaldehyde, acetone or the like, with aliphatic or aromatic amines oramides, for example urea, thiourea, guanidine and their derivatives,dicyandiamide, aniline, methyl aniline, diphenylamine, benzyl aniline,,B-naphthylamine, para-toluenesulphonamide or other aromaticsulphonamides or N-alkyl or other derivatives thereof. ther group ofmaterials available is the condensation products of gelatine, casein orother albumenoid compounds with formaldehyde for example. The inventionis not, however, confined to condensation products of aldehydic orketonic bodies with nitrogen-containing organic compounds, since anyother nitrogen-containing resinous or highly complex organic compound issuitable. For example, the condensation prodnet of phenol with methylenediphenyldiamine I A furmay be employed. In most cases. condensation toproduce the above mentioned resinous materials is most advantageouslycarried out in the presence of catalysts, which may be alkaline, acid orneutral.

It is desirable that the nitrogenous product produced by interaction ofthe reagents on the material shall be substantially insoluble in wateror in aqueous reagents which are customarily applied to the textilematerials as, for example, in dyeing or scouring operations.

The reagents necessary may be applied together to the materials or maybe applied separately or in any suitable combination. For example thefabric may be first impregnated with a catalyst and the mixture of twobodies for condensation subsequently applied, or alternatively themixture of the two bodies to undergo condensation may be first appliedand the catalyst subsequently applied. One of the bodies to be condensedmay be applied with the catalyst and the other body applied separately.This last alternative is specially useful where one of the reagents isto be applied in the form of vapor as may bethe case, for example, withformaldehyde.

Reaction between the resin-forming reagents is conveniently effected byheating the materials impregnated with the reagents. Steaming may beutilized if desired.

The following examples illustrate the invention.

- Example 1 A cellulose or cellulose derivative fiber or fabric isimpregnated locally or printed or treated in an analogous manner with amixture having the following composition, the parts being by weight:

Grams Thiourea 100-150 Water 250-300 40% formaldehyde 550 Formic acid 50The material is then dried at 80 during an hour or two until thecondensation has given rise to a product insoluble in boiling water.

The material thus treated can then be dyed by any suitable process witha direct dyestufi which reserves animal fibers. The dyebath may containany of the usual assistants, for example a sulphonated higher fattyalcohol or other wetting agent or sodium sulphate. The untreated partsof the material take the color normally while the treated parts act as areserve against the color so that a white pattern on a coloredbackground is obtained.

In a similar way the material may be dyed with an acid color by choosingan acid dyestuif which has good reserve properties for cotton fibers.The treated parts only are dyed so that a colored pattern on a whitebackground is obtained.

Again, basic dyestuffs may be employed to color the material. In thiscase, natural or regenerated cellulose materials and also cellulosederivative materials having a certain affinity for these colors, theuntreated parts also take some of the color while the treated parts havetheir afiinity for the color enhanced so that deep designs on a palerbackground are obtained.

A plurality of acid, basic and cotton colors may be applied to thematerials in succession or, where they are compatible, in a single bath,so as to obtain differential colorations on the design and background.

Example 2 A cellulose or cellulose derivative fiber or fabric isimpregnated locally or printed or treated in an analogous manner withthe following mixture:

Grams Dicyandiamide 100-200 Ammonium sulphocyanide 40% formaldehyde 780The sequence of operations is carried out as indicated in Example 1.

In the above examples, any other suitable nitrogen-containing bodies maybe substituted for the agents therein mentioned. In addition,penetrating agents, plasticizers or softeners such as glycerine, oils,sulphonated fatty oils or the like may be added to the mixture. Latex orother suitable agents having the effect of increasing the fixation ofthe material may likewise be pres- 1' ent. If desired, the mixture forproducing the condensation product on the material may contain thedyestuif.

Example 3 The cellulose or cellulose derivative fiber or fabric isimpregnated locally or printed or treated in an analogous manner withthe following mixture:

Grams Urea M 100-200 Dicyandiamide 60 Glycerine 60 Alkaline or alkalineearth sulphocyanide 20 40% formaldehyde 660 The sequence of operationsis effected as indicated in Example 1.

Example 4 A fabric of natural silk or regenerated artificial silk isprinted with the following mixture:-

Urea or thiourea "grams" 100 40% formaldehyde ccs 300-500 Formic acid do50 Dyestuff "grams" 10- 50 Water and thickener sufficient to make 1000grams in all.

After drying the fabric is stoved at 110 C. for 1-2 hours and thenwashed with water. By mixing in the fabric or other material naturalsilk, wool or other animal fibers, effects due to the weaving or otherarrangement of these animal fibers in the goods may be superimposed uponthe effects described above.

The following are examples of coloring mat ters which may be usedaccording to the inven- Basic coloring matters Color index No. RhodulineYellow 815 Acridine Orange 788 Chrysoidine 20 Methylene Blue 922Toluidine Blue. 925 Rhoduline Blue 658 Victoria Blue- 729 MalachiteGreen 657 Rhodamine 6G 752 Rhodamine B 749 Methylene Violet 842 Directcolors reserved by the complex nitrogenous compounds Diphenyl FastYellow 632 IBenzo Fast Scarlet 838---; 326

Paramine Orange 415 Benzo Fast Orange W8 326 Direct Blue 23 406 DirectSky Blue 520 Direct Blue RWS 512 Direct Pink 126 Direct Black BH 401 Theterm nitrogenous resin" as employed hereinafter in the claims is to beconstrued as including within its scope condensation products ofgelatine, casein or other albumenoid compounds with formaldehyde orother aldehydes.

What I claim and desire to secure by Letters Patent is:--

1. Process of coloring textile materials, which comprises impregnatingat least part of the material with reagents capable of reacting to yielda nitrogenous resin and then effecting formation of compound from saidreagents on the material, and dyeing the materials by applying adyestufl to at least a portion of the impregnated part at the earliestat the time of applying one of said reagents.

2. Process of coloring cellulosic textile materials, which comprisesimpregnating at least part of the material with reagents capable ofreacting to yield a nitrogenous resin and effecting formation of saidresin from said reagents on the material, and dyeing the materials byapplying a dyestuff to at least a portion of the impregnated part at theearliest at the time of applying one of said reagents.

3. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the fabric with reagents capable ofreacting to yield a nitrogenous resin, effecting formation of saidnitrogenous resin on the materials, and thereafter dyeing the materialwith a dyestufl having afilnity for animal fibers.

reacting with formaldehyde to yield a nitrogenous resin, effectingformation of said nitrogenous resin on the material, and thereafterdyeing the material with a dyestuif having affinity for animal fibers.

5. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the material with a mixturecontaining formaldehyde and urea. heating the fabric to effect resinformation on the material by interaction of the formaldehyde and urea,and dyeing the material with a dyestuif having affinity for animalfibers. v

6. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the fabric with a mixture ofreagents capable of reacting to yield a nitrogenous resin. effectingformation of said nitrogenous resin on the material, and thereafterdyeing the material with a dyestufl which has ailinity for cellulosematerials but which resists animal fibers.

7. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the fabric with a mixture offormaldehyde and an aromatic amine, effecting formation of a nitrogenousresin on the material by interaction of the formaldehyde and aromaticamine, and thereafter dyeing the material with a dyestuff having amnityfor animal fibers.

8. Process of coloring textile fabric, which comprises locallyimpregnating the fabric with a mixture containing reagents capable ofreacting to form a nitrogenous resin and also containing! a dyestuffhaving afllnity for animal fibers, and thereafter effecting reactionbetween the said reagents to form a nitrogenous resin on the material.

9. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the fabric with a mixturecontaining reagents capable of reacting to form a nitrogenous resin andalso containing a dyestuif having aflinity for animal fibers, andthereafter effecting reaction between the said reagents to form anitrogeneous resin on the material.

10. Process of coloring textile fabric comprising cellulosefilaments,which comprises locally impregnating the fabric with a mixturecontaining a dyestuff selected from the group consisting of acid andbasic dyestuffs, formaldehyde, and urea, and thereafter heating thefabric to produce a resin on the material by interaction of the urea andformaldehyde.

11. Process of coloring textile fabric containing cellulose filaments,which comprises locally impregnating the fabric with analbuminoid andformaldehyde and causing said albuminoid and formaldehyde to interactthereon, and thereafter dyeing the material with a dyestufl havingaffinity for animal fibers.

GEORGES RIVAT.

GERTIFI GATE OF CORRECTION Patent No. 2,12%152; July 5, 1938.

' GEORGES RIVATO It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionas follows: Page 5, first column, line 57, claim 1, before compoundinsert the word said; and that the said Letters Patent should be readwith this correction therein that the same may conform to the record ofthe case in the Patent Office.

Signed and sealed. thie 9th day of August, A. D, 1958.0

Leslie Frazer (Seal) Acting Commissioner of Patents.

